Biocide Compositions Comprising Derivatives Of Pyroglutamic Acid

ABSTRACT

Described are agrochemical compositions, comprising (a) esters and/or amides of pyroglutamic acid, and (b) biocides. The compositions are clear and exhibit an improved stability even when stored at temperatures between 5° and 40° C. over a longer period.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional application of U.S. application Ser. No. 13/515,115, filed Jun. 11, 2012, which is the National Stage entry of PCT/EP2010/007404, filed on Dec. 6, 2010, which claims priority to European Patent application number 09015513.6, filed on Dec. 15, 2009, the contents of which are incorporated herein by reference in their entireties.

TECHNICAL FIELD

The present invention relates to the area of agrochemicals and refers to biocide compositions comprising certain esters and/or amides and their use as solvents or dispersants for biocides.

BACKGROUND

Biocides, and in particular pesticides such as fungicides, insecticides and herbicides, are important auxiliary agents for agriculture in order to protect and to increase crops. Depending on the various and often very specific needs a magnitude of actives exist which show very different chemical structures and behaviours. Nevertheless, it is well known from the state of the art that it remains difficult to prepare aqueous solutions of these actives which are exhibiting a satisfying stability, especially if stored at very low or elevated temperatures over a longer period. As a matter of fact, the solutions show a strong tendency to either separate or to form crystals, which makes it necessary to re-disperse the actives in the compositions prior to every application in order to obtain a homogenous product. Due to the fact that in spray equipments, which are customarily used for the application of aqueous formulations of plant treatment agents, several filters and nozzles are present, an additional problem appears which is related to the blocking of these filters and nozzles as a result of crystallizing active compound during the application of aqueous spray liquors based on solid active compounds.

European patent application EP 0453899 B1 (Bayer) discloses the use of dimethylamides derived from saturated C₆-C₂₀ fatty acids as crystallisation inhibitors for azol derivatives which can be applied as fungicides. Unfortunately, the dimethylamides suggested in the patent are useful for a limited number of actives. Even in the case of azols and azol derivatives, the ability to inhibit unwanted crystallisation is limited to ambient temperatures, while the products are close to being useless in the case where the solutions have to be used at temperatures of about 5 to 10° C.

The problem underlying the present invention has been to identify suitable new solvents for developing new biocide compositions allowing preparing products with equal or higher contents of actives than obtainable in the market. The new solvents need to be safe and environmentally friendly and should allow obtaining concentrated biocide compositions (on average more than 25% active matter) regardless of the chemical structure of the biocide, In particular, the compositions should exhibit improved solubilisation power, storage stability and reduced tendency to form crystals for a wide range of biocides within a temperature range between 5 and 40° C. Finally, another object of the invention has been to design emulsifiable concentrates formulations with specific co-solvents and emulsifier systems providing superior emulsion stability, in particular with respect to opacity and layering.

SUMMARY

Embodiments of the present invention are directed toward a biocide composition comprising (a) an ester and/or amide of pyroglutamic acid, and (b) a biocide.

In one or more embodiments, component (a) comprises an ester and/or an amide according to the general formula (I), wherein X is O[AO]_(n)R¹ or NR²R³, [AO] is a C₂-C₄ alkylene oxide unit, n is 0 or an integer of 1 to 100, R¹ represents hydrogen, an alkyl or alkenyl radical having 1 to 22 carbon atoms or a (tetrahydro)furfuryl residue, and R² and R³ represent independently from each other hydrogen or an alkyl or alkenyl radical having 1 to 22 carbon atoms.

In one or more embodiments, component (a) comprises an ester selected from the group consisting of pyroglutamic acid methyl ester, pyroglutamic acid ethyl ester, pyroglutamic acid propyl ester(s), pyroglutamic acid butyl ester(s), pyroglutamic acid n-octyl ester, pyroglutamic-2-ethylhexyl ester, pyroglutamic acid furfuryl ester, pyroglutamic acid tetrahydrofurfuryl ester, and mixtures thereof.

In one or more embodiments, component (a) comprises an amide selected from the group consisting of pyroglutamic acid dimethyl amide, pyroglutamic acid diethyl amide, pyroglutamic acid dipropyl amide, pyroglutamic acid dibutyl amide, pyroglutamic acid di-n-octyl amide, pyroglutamic acid di-2-ethylhexyl amide, and mixtures thereof.

In one or more embodiments, the biocide is selected from the group consisting of herbicides, fungicides, insecticides, and plant growth regulators

In a specific embodiment, the biocide is selected from the group consisting of azoles, oxyfluorfen, propanil, chlorpyrifos, bifenthrin, novaluron, phenmedipham, deltamethrin, acetochlore, lambdacyhalothrin, glyphosate and its salts, and glufosinate and its salts.

In one or more embodiments, the composition further comprises an oil component or a co-solvent. In one or more embodiments, the composition further comprises an emulsifier.

In one or more embodiments, the composition comprises (a) 0.1% b.w. to 99% b.w. an ester and/or an amide of pyroglutamic acid, (b) 1% b.w. to 99.1% b.w. a biocide, (c) 0% b.w. to 50% b.w. an oil component or a co-solvent, and (d) 0% b.w. to 15% b.w. an emulsifier, with the proviso that the amounts add, optionally with water and/or polyols, to 100% b.w.

In a specific embodiment, the composition has an active matter content of 5% b.w. to 50% b.w.

In one or more embodiments, the composition comprises The composition of claim 19, wherein the composition comprises (a) 0.1% b.w. to 99% b.w. an ester and/or amide according to the general formula (I), wherein X is O[AO]_(n)R¹ or NR²R³, [AO] is a C₂-C₄ alkylene oxide unit, n is 0 or an integer of 1 to 100, R¹ represents hydrogen, an alkyl or alkenyl radical having 1 to 22 carbon atoms or a (tetrahydro)furfuryl residue, and R² and R³ represent independently from each other hydrogen or an alkyl or alkenyl radical having 1 to 22 carbon atoms; (b) 1% b.w. to 99.1% b.w. a biocide; (c) 0% b.w. to 50% b.w. an oil component or a co-solvent; and (d) 0% b.w. to 15% b.w. an emulsifier, with the proviso that the amounts add, optionally with water and/or polyols, to 100% b.w. Component (a) can comprise an ester selected from the group consisting of pyroglutamic acid methyl ester, pyroglutamic acid ethyl ester, pyroglutamic acid propyl ester(s), pyroglutamic acid butyl ester(s), pyroglutamic acid n-octyl ester, pyroglutamic-2-ethylhexyl ester, pyroglutamic acid furfuryl ester, pyroglutamic acid tetrahydrofurfuryl ester, and mixtures thereof. Component (a) can comprise an amide selected from the group consisting of pyroglutamic acid dimethyl amide, pyroglutamic acid diethyl amide, pyroglutamic acid dipropyl amide, pyroglutamic acid dibutyl amide, pyroglutamic acid di-n-octyl amide, pyroglutamic acid di-2-ethylhexyl amide, and mixtures thereof. The biocide can be selected from the group consisting of herbicides, fungicides, insecticides, and plant growth regulators. The biocide can be selected from the group consisting of azoles, oxyfluorfen, propanil, chlorpyrifos, bifenthrin, novaluron, phenmedipham, deltamethrin, acetochlore, lambdacyhalothrin, glyphosate and its salts, and glufosinate and its salts. The composition can further comprise an oil component or a co-solvent. The composition can also further comprise an emulsifier.

A second aspect of the present invention is directed to a method of dispersing a biocide, the method comprising using an ester and/or amide of pyroglutamic acid as a solvent or dispersant.

DETAILED DESCRIPTION

The present invention provides biocide compositions, comprising

-   -   (a) esters and/or amides of pyroglutamic acid,     -   (b) biocides, and optionally     -   (c) oil components or co-solvents and/or     -   (d) emulsifiers.

Surprisingly it has been observed that esters and amides of pyroglutamic acid, specifically, in one or more embodiments, the dimethyl ester, the dibutyl ester, the 2-ethylhexyl ester, the furfuryl ester and the dimethylamide show improved solubilising power compared to other derivatives from fatty acids as known from the state of the art. Applicant has found that the pyroglutamic acid derivatives are able to dissolve or disperse a wide range of biocides even under drastic conditions, which means storage times of at least 4 weeks at temperatures between 5 and 40° C. without phase separation or sedimentation. Adding oil components as co-solvents, especially those having an ester structure to the compositions lead to emulsifiable concentrates formulations showing increased emulsion behaviour and stability, in particular with respect to opacity and layering.

Esters and Amides of Pyroglutamic Acid

In one or more embodiments, esters and amides (component a) are derived from pyroglutamic acid, which is also known as pidolic acid. The acid and its derivatives are available in the market and widely known as dietary supplements, in particular for the United States. In one or more embodiments, the species follow general formula (I)

wherein X is O[AO]_(n)R¹ or NR²R³, [AO] is a C₂-C₄ alkylene oxide unit, n is 0 or an integer of 1 to 100, in a specific embodiment n is an integer of 2 to 50, and in a more specific embodiment n is an integer of 5 to 25, R¹ represents hydrogen, an alkyl or alkenyl radical having 1 to 22 carbon atoms, in a specific embodiment R¹ represents hydrogen, an alkyl or alkenyl radical having 1 to 8 carbon atoms, and in a more specific embodiment R¹ represent hydrogen, an alkyl or alkenyl radical having 1 to 4 carbon atoms or a (tetrahydro)furfuryl residue, and R² and R³ represent independently from each other hydrogen or an alkyl or alkenyl radical having 1 to 22 carbon atoms, in a specific embodiment R² and R³ represent independently from each other hydrogen or an alkyl or alkenyl radical having 1 to 8 carbon atoms, and in a more specific embodiment R² and R³ represent independently from each other hydrogen or an alkyl or alkenyl radical having 1 to 4 carbon atoms. In one or more embodiments, the species exhibiting the best performance in dissolving or dispersing a wide number of different biocides over a long period and both at low and high temperatures are pyroglutamic acid methyl ester, pyroglutamic acid ethyl ester, pyroglutamic acid propyl ester(s), pyroglutamic acid butyl ester(s), pyroglutamic acid n-octyl ester, pyroglutamic-2-ethylhexyl ester, pyroglutamic acid furfuryl ester, pyroglutamic acid tetrahydrofurfuryl ester, pyroglutamic acid dimethyl amide, pyroglutamic acid diethyl amide, pyroglutamic acid dipropyl amide, pyroglutamic acid dibutyl amide, pyroglutamic acid di-n-octyl amide, pyroglutamic acid di-2-ethylhexyl amide, pyroglutamic acid morpholine amide and their mixtures. As far as alkyl esters or amides are concerned, it should be noted that the citation of one of the possible isomers exemplifies all possible isomers. As far as the esters are concerned, these compounds may also include polyalkylene glycol units, in particular ethylene glycol or propylene glycol units or their mixtures, obtained for example by esterifying the pyroglutamic acid with the respective alkoxylated alcohol. Similar products are disclosed for example in EP 1951666 B1 assigned to Clariant.

Biocides

In one or more embodiments, a biocide (component b) is a plant protection agent, more particular a chemical substance capable of killing different forms of living organisms used in fields such as medicine, agriculture, forestry, and mosquito control. Also counted under the group of biocides are so-called plant growth regulators. Usually, biocides are divided into two sub-groups:

-   -   pesticides, which includes fungicides, herbicides, insecticides,         algicides, moluscicides, miticides and rodenticides, (here, The         Pesticide Handbook, 14th edition, BCPC 2006 is included as a         reference) and     -   antimicrobials, which includes germicides, antibiotics,         antibacterials, antivirals, antifungals, antiprotozoals and         antiparasites.

Biocides can also be added to other materials (typically liquids) to protect the material from biological infestation and growth. For example, certain types of quaternary ammonium compounds (quats) can be added to pool water or industrial water systems to act as an algicide, protecting the water from infestation and growth of algae.

Pesticides

The U.S Environmental Protection Agency (EPA) defines a pesticide as “any substance or mixture of substances intended for preventing, destroying, repelling, or mitigating any pest”. A pesticide may be a chemical substance or biological agent (such as a virus or bacteria) used against pests including insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms) and microbes that compete with humans for food, destroy property, spread disease or are a nuisance. In the following examples, pesticides suitable for the agrochemical compositions are given:

Fungicides.

A fungicide is one of three main methods of pest control—the chemical control of fungi in this case. Fungicides are chemical compounds used to prevent the spread of fungi in gardens and crops. Fungicides are also used to fight fungal infections. Fungicides can either be contact or systemic. A contact fungicide kills fungi when sprayed on its surface. A systemic fungicide has to be absorbed by the fungus before the fungus dies. Examples for suitable fungicidesencompass the following chemical classes and corresponding examples:

-   -   Aminopyrimidines such as bupirimate,     -   Anilinopyrimidines such as cyprodinil, mepanipyrim,         pyrimethanil,     -   Heteroaromatics such as hymexazol,     -   Heteroaromatic hydrocarbons such as etridiazole,     -   Chlorophenyls/Nitroanilines such as chloroneb, dicloran,         quintozene, tecnazene, tolclofos-methyl,     -   Benzamide fungicides such as zoxamide,     -   Benzenesulfonamides such as flusulfamide,     -   Benzimidazoles such as acibenzolar, benomyl, benzothiazole,         carbendazim, fuberidazole, metrafenone, probenazole,         thiabendazole, triazoxide, and benzimidazole precursor         fungicides,     -   Carbamates such as propamocarb, diethofencarb,     -   Carboxamides such as boscalid, diclocymet, ethaboxam,         flutolanil, penthiopyrad, thifluzamide     -   Chloronitriles such chlorothalonil,     -   Cinnamic acid amides such as dimethomorph, flumorph,     -   Cyanoacetamide oximes such as cymoxanil,     -   Cyclopropancarboxamides such as carpropamid,     -   Dicarboximides such as iprodione, octhilinone, procymidone,         vinclozolin     -   Dimethyldithiocarbamates such ferbam, metam, thiram, ziram,     -   Dinitroanilines such as fluazinam,     -   Dithiocarbamates such as mancopper, mancozeb, maneb, metiram,         nabam, propineb, zineb,     -   Dithiolanes such as isoprothiolane,     -   Glucopyranosyl antibiotics such as streptomycin, validamycin,     -   Guanidines such as dodine, guazatine, iminoctadine,     -   Hexopyranosyl antibiotics such as kasugamycin,     -   Hydroxyanilides such as fenhexamid,     -   Imidazoles such as imazalil, oxpoconazole, pefurazoate,         prochloraz, triflumizole,     -   Imidazolinones such as fenamidone,     -   Inorganics such as Bordeaux mixture, copper hydroxide, copper         naphthenate, copper oleate, copper oxychloride, copper(II)         sulfate, copper sulfate, copper(II) acetate, copper(II)         carbonate, cuprous oxide, sulfur,     -   Isobenzofuranones such as phthalide,     -   Mandelamides such as mandipropamide,     -   Morpholines such as dodemorph, fenpropimorph, tridemorph,         fenpropidin, piperalin, spiroxamine, aldimorph     -   Organotins such as fentin,     -   Oxazolidinones such as oxadixyl,     -   Phenylamides such as benalaxyl, benalaxyl-M, furalaxyl,         metalaxyl, metalaxyl-M, ofurace,     -   Phenylpyrazoles such as fipronil,     -   Phenylpyrroles such as fludioxonil,     -   Phenylureas such as pencycuron,     -   Phosphonates such fosetyl,     -   Phthalamic acids such as tecloftalam,     -   Phthalimides such as captafol, captan, folpet,     -   Piperazines such as triforine,     -   Propionamides such as fenoxanil,     -   Pyridines such as pyrifenox,     -   Pyrimidines such as fenarimol, nuarimol,     -   Pyrroloquinolinones such as pyroquilon,     -   Qils such as cyazofamid,     -   Quinazolinones such as proquinazid,     -   Quinolines such as quinoxyfen,     -   Quinones such as dithianon,     -   Sulfamides such as tolylfluanid, dichlofluanid,     -   Strobilurines such as azoxystrobin, dimoxystrobin, famoxadone,         fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin,         pyraclostrobin, trifloxystrobin, orysastrobin,     -   Thiocarbamates such as methasulfocarb,     -   Thiophanates such as thiophanate-methyl,     -   Thiophencarboxamides such silthiofam,     -   Triazole fungicides such as azaconazole, bitertanol,         bromuconazole, cyproconazole, difenoconazole, diniconazole,         epoxiconazole, fenbuconazole, fluquinconazole, flusilazole,         flutriafol, fluotrimazole, hexaconazole, imibenconazole,         ipconazole, metconazole, myclobutanil, penconazole,         propiconazole, prothioconazole, simeconazole, tebuconazole,         tetraconazole, triadimefon, triadimenol, triticonazole,         quinconazole     -   Triazolobenzothidazoles such as tricyclazole,     -   Valinamide carbamates such as iprovalicarb, benthiavalicarb     -   Fluopicolide     -   Pentachlorophenol         and mixtures thereof.

Herbicides.

An herbicide is a pesticide used to kill unwanted plants. Selective herbicides kill specific targets while leaving the desired crop relatively unharmed. Some of these act by interfering with the growth of the weed and are often based on plant hormones. Herbicides used to clear waste ground are nonselective and kill all plant material with which they come into contact. Herbicides are widely used in agriculture and in landscape turf management. They are applied in total vegetation control (TVC) programs for maintenance of highways and railroads. Smaller quantities are used in forestry, pasture systems, and management of areas set aside as wildlife habitat. In general, active ingredients representing including various chemical classes and corresponding examples can be used

-   -   Anilides such as propanil     -   Aryloxycarboxylic acids e.g. MCPA-thioethyl     -   Aryloxyphenoxypropionates e.g. clodinafop-propargyl,         cyhalofop-butyl, diclofops, fluazifops, haloxyfops, quizalofops,     -   Chloroacetamides e.g. acetolochlor, alachlor, butachlor,         dimethenamid, metolachlor, propachlor     -   Cyclohexanedione oximes e.g. clethodim, sethoxydim, tralkoxydim,     -   Benzamides such as isoxaben     -   Benzimidazoles such as dicamba, ethofumesate     -   Dinitroanilines e.g. trifluralin, pendimethalin,     -   Diphenyl ethers e.g. aclonifen, oxyfluorfen,     -   The glycine derivative glyphosate, a systemic nonselective (it         kills any type of plant) herbicide used in no-till burndown and         for weed control in crops that are genetically modified to         resist its effects,     -   Hydroxybenzonitriles e.g. bromoxynil,     -   Imidazolinones e.g. fenamidone, imazapic, imazamox, imazapic,         imazapyr, imazaquin,     -   Isoxazolidinones e.g. clomazone     -   Paraquat as bypyridylium,     -   Phenyl carbamates e.g. desmedipham, phenmedipham,     -   Phenylpyrazoles e.g. pyraflufen-ethyl     -   Phenylpyrazolines e.g. pinoxaden,     -   Pyridinecarboxylic acids or synthetic auxins e.g. picloram,         clopyralid, and triclopyr,     -   Pyrimidinyloxybenzoics e.g. bispyrtbac-sodium     -   Sulfonyureas e.g. amidosulfuron, azimsulfuron,         bensulfuron-methyl, chlorsulfuron, flazasulfuron, foramsulfuron,         flupyrsulfuron-methyl-sodium, nicosulfuron, rimsulfuron,         sulfosulfuron, tribenuron-methyl, trifloxysurlfuron-sodium,         triflusulfuron, tritosulfuron,     -   Triazolopyrimidines e.g. penoxsulam, metosulam, florasulam,     -   Triketones e.g. mesotriones, sulcotrione,     -   Ureas e.g. diuron, linuron,     -   Phenoxycarboxylic acids such as 2,4-D, MCPA, MCPB, mecoprops,     -   Triazines such as atrazine, simazine, terbuthylazine,         and mixtures thereof.

Insecticides.

An insecticide is a pesticide used against insects in all developmental forms. They include ovicides and larvicides used against the eggs and larvae of insects. Insecticides are used in agriculture, medicine, industry and the household. In the following, suitable chemical classes and examples of insecticides are mentioned:

-   -   Abamectin, emamectin,     -   Anthranilic diamides such as rynaxypyr     -   Synthetic auxins Duch as avermectin,     -   Amidines such as amitraz,     -   Anthranilic diamide Duch as rynaxypyr,     -   Carbamates such as aldicarb, carbofuran, carbaryl, methomyl,         2-(1-methylpropyl)phenyl methylcarbamate,     -   Chlorinated insecticides such as, for example, Camphechlor, DDT,         Hexachlorocyclohexane, gamma-Hexachlorocyclohexane,         Methoxychlor, Pentachlorophenol, TDE, Aldrin, Chlordane,         Chlordecone, Dieldrin, Endosulfan, Endrin, Heptachlor, Mirex,     -   Juvenile hormone mimics such as pyriproxyfen,     -   Neonicotinoids such as imidacloprid, clothianidin, thiacloprid,         thiamethoxam,     -   Organophosphorus compounds such as acephate, azinphos-methyl,         bensulide, chlorethoxyfos, chlorpyrifos, chlorpyriphos-methyl,         diazinon, dichlorvos (DDVP), dicrotophos, dimethoate,         disulfoton, dthoprop, fenamiphos, fenitrothion, fenthion,         fosthiazate, malathion, methamidophos, methidathion,         methyl-parathion, mevinphos, naled, omethoate,         oxydemeton-methyl, parathion, phorate, phosalone, phosmet,         phostebupirim, pirimiphos-methyl, profenofos, terbufos,         tetrachlorvinphos, tribufos, trichlorfon,     -   Oxadiazines such as indoxacarb,     -   Plant toxin derived compounds such as derris (rotenone),         pyrethrum, neem (azadirachtin), nicotine, caffeine,     -   Pheromones such cuellure, methyl eugenol,     -   Pyrethroids such as, for example, allethrin, bifenthrin,         deltamethrin, permethrin, resmethrin, sumithrin, tetramethrin,         tralomethrin, transfluthrin,     -   Selective feeding blockers such as flonicamid, pymetrozine,     -   Spinosyns e.g. spinosad         and mixtures thereof.

Plant Growth Regulators.

Plant hormones (also known as phytohormones) are chemicals that regulate plant growth. Plant hormones are signal molecules produced within the plant, and occur in extremely low concentrations. Hormones regulate cellular processes in targeted cells locally and when moved to other locations, in other locations of the plant. Plants, unlike animals, lack glands that produce and secrete hormones. Plant hormones shape the plant, affecting seed growth, time of flowering, the sex of flowers, senescence of leaves and fruits. They affect which tissues grow upward and which grow downward, leaf formation and stem growth, fruit development and ripening, plant longevity and even plant death. Hormones are vital to plant growth and lacking them, plants would be mostly a mass of undifferentiated cells. In the following, suitable plant growth regulators are mentioned:

-   -   Aviglycine,     -   Cyanamide,     -   Gibberellins such gibberellic acid,     -   Quaternary ammoniums such as chlormequat chloride, mepiquat         chloride,     -   Ethylene generators such ethephone,

Rodenticides.

Rodenticides are a category of pest control chemicals intended to kill rodents. Rodents are difficult to kill with poisons because their feeding habits reflect their place as scavengers. They would eat a small bit of something and wait, and if they do not get sick, they would continue eating. An effective rodenticide must be tasteless and odorless in lethal concentrations, and have a delayed effect. In the following, examples for suitable rodenticides are given:

-   -   Anticoagulants are defined as chronic (death occurs after 1-2         weeks post ingestion of the lethal dose, rarely sooner),         single-dose (second generation) or multiple dose (first         generation) cumulative rodenticides. Fatal internal bleeding is         caused by lethal dose of anticoagulants such as brodifacoum,         coumatetralyl or warfarin. These substances in effective doses         are antivitamins K, blocking the enzymes         K₁-2,3-epoxide-reductase (this enzyme is preferentially blocked         by 4-hydroxycoumarin/4-hydroxythiacoumarin derivatives) and         K₁-quinone-reductase (this enzyme is preferentially blocked by         indandione derivatives), depriving the organism of its source of         active vitamin K₁. This leads to a disruption of the vitamin K         cycle, resulting in an inability of production of essential         blood-clotting factors (mainly coagulation factors II         (prothrombin), VII (proconvertin), IX (Christmas factor) and X         (Stuart factor)). In addition to this specific metabolic         disruption, toxic doses of         4-hydroxycoumarin/4-hydroxythiacoumarin and indandione         anticoagulants are causing damage to tiny blood vessels         (capillaries), increasing their permeability, causing diffuse         internal bleedings (haemorrhagias). These effects are gradual;         they develop in the course of days and are not accompanied by         any nociceptive perceptions, such as pain or agony. In the final         phase of intoxication the exhausted rodent collapses in         hypovolemic circulatory shock or severe anemia and dies calmly.         Rodenticidal anticoagulants are either first generation agents         (4-hydroxycoumarin type: warfarin, coumatetralyl; indandione         type: pindone, diphacinone, chlorophacinone), generally         requiring higher concentrations (usually between 0.005 and         0.1%), consecutive intake over days in order to accumulate the         lethal dose, poor active or inactive after single feeding and         less toxic than second generation agents, which are derivatives         of 4-hydroxycoumarin (difenacoum, brodifacoum, bromadiolone and         flocoumafen) or 4-hydroxy-1-benzothiin-2-one         (4-hydroxy-1-thiacoumarin, sometimes incorrectlly referred to as         4-hydroxy-1-thiocoumarin, for reason see heterocyclic         compounds), namely difethialone. Second generation agents are         far more toxic than first generation agents, they are generally         applied in lower concentrations in baits (usually in the order         of 0.001-0.005%), and are lethal after single ingestion of bait         and are effective also against strains of rodents that have         become resistant against first generation anticoagulants; thus         the second generation anticoagulants are sometimes referred to         as “superwarfarins”. Sometimes, anticoagulant rodenticides are         potentiated by an antibiotic, most commonly by sulfaquinoxaline.         The aim of this association (e.g. warfarin         0.05%+sulfaquinoxaline 0.02%, or difenacoum         0.005%+sulfaquinoxaline 0.02% etc.) is that the         antibiotic/bacteriostatic agent suppresses intestinal/gut         symbiotic microflora that represents a source of vitamin K. Thus         the symbiotic bacteria are killed or their metabolism is         impaired and the production of vitamin K by them is diminuted,         an effect which logically contributes to the action of         anticoagulants. Antibiotic agents other than sulfaquinoxaline         may be used, for example co-trimoxazole, tetracycline, neomycin         or metronidazole. A further synergism used in rodenticidal baits         is that of an association of an anticoagulant with a compound         with vitamin Dactivity, i.e. cholecalciferol or ergocalciferol         (see below). A typical formula used is, e. g., warfarin         0.025-0.05%+cholecalciferol 0.01%. In some countries there are         even fixed three-component rodenticides, i.e.         anticoagulant+antibiotic+vitamin D, e. g. difenacoum         0.005%+sulfaquinoxaline 0.02%+cholecalciferol 0.01%.         Associations of a second-generation anticoagulant with an         antibiotic and/or vitamin D are considered to be effective even         against the most resistant strains of rodents, though some         second generation anticoagulants (namely brodifacoum and         difethialone), in bait concentrations of 0.0025-0.005% are so         toxic that no known resistant strain of rodents exists and even         rodents resistant against any other derivatives are reliably         exterminated by application of these most toxic anticoagulants.

Vitamin K₁ has been suggested and successfully used as an antidote for pets or humans, which/who were either accidentally or intentionally (poison assaults on pets, suicidal attempts) exposed to anticoagulant poisons. In addition, since some of these poisons act by inhibiting liver functions and in progressed stages of poisoning, several blood-clotting factors as well as the whole volume of circulating blood lacks, a blood transfusion (optionally with the clotting factors present) can save a person's life who inadvertently takes them, which is an advantage over some older poisons.

-   -   Metal phosphides have been used as a means of killing rodents         and are considered single-dose fast acting rodenticides (death         occurs commonly within 1-3 days after single bait ingestion). A         bait consisting of food and a phosphide (usually zinc phosphide)         is left where the rodents can eat it. The acid in the digestive         system of the rodent reacts with the phosphide to generate the         toxic phosphine gas. This method of vermin control has possible         use in places where rodents are resistant to some of the         anticoagulants, particularly for control of house and field         mice; zinc phosphide baits are also cheaper than most         second-generation anticoagulants, so that sometimes, in cases of         large infestation by rodents, their population is initially         reduced by copious amounts of zinc phosphide bait applied, and         the rest of the population that survived the initial fastacting         poison is then eradicated by prolonged feeding on anticoagulant         bait. Inversely, the individual rodents that survived         anticoagulant bait poisoning (rest population) can be eradicated         by pre-baiting them with nontoxic bait for a week or two (this         is important to overcome bait shyness, and to get rodents used         to feeding in specific areas by offering specific food,         especially when eradicating rats) and subsequently applying         poisoned bait of the same sort as used for pre-baiting until all         consumption of the bait ceases (usually within 2-4 days). These         methods of alternating rodenticides with different modes of         action provides a factual or an almost 100% eradication of the         rodent population in the area if the acceptance/palatability of         bait is good (i.e., rodents readily feed on it).     -   Phosphides are rather fast acting rat poisons, resulting in that         the rats are dying usually in open areas instead of the affected         buildings. Typical examples are aluminum phosphide (fumigant         only), calcium phosphide (fumigant only), magnesium phosphide         (fumigant only) and zinc phosphide (in baits) Zinc phosphide is         typically added to rodent baits in amounts of around 0.75-2%.         The baits have a strong, pungent garlic-like odor characteristic         for phosphine liberated by hydrolysis. The odor attracts (or, at         least, does not repulse) rodents, but has a repulsive effect on         other mammals; birds, however (notably wild turkeys), are not         sensitive to the smell and feed on the bait thus becoming         collateral damage.     -   Hypercalcemia. Calciferols (vitamins D), cholecalciferol         (vitamin D₃) and ergocalciferol (vitamin D₂) are used as         rodenticides, which are toxic to rodents for the same reason         that they are beneficial to mammals: they are affecting calcium         and phosphate homeostasis in the body. Vitamins D are essential         in minute quantities (few IUs per kilogram body weight daily,         which is only a fraction of a milligram), and like most fat         soluble vitamins they are toxic in larger doses as they readily         result in the so-called hypervitaminosis, which is, simply said,         poisoning by the vitamin. If the poisoning is severe enough         (that is, if the dose of the toxicant is high enough), it         eventually leads to death. In rodents consuming the rodenticidal         bait it causes hypercalcemia by raising the calcium level,         mainly by increasing calcium absorption from food, mobilising         bone-matrix-fixed calcium into ionised form (mainly         monohydrogencarbonate calcium cation, partially bound to plasma         proteins, [CaHCO₃]⁺), which circulates dissolved in the blood         plasma, and after ingestion of a lethal dose the free calcium         levels are raised sufficiently so that blood vessels, kidneys,         the stomach wall and lungs are mineralised/calcificated         (formation of calcificates, crystals of calcium salts/complexes         in the tissues thus damaging them), leading further to heart         problems (myocard is sensitive to variations of free calcium         levels that are affecting both myocardial contractibility and         excitation propagation between atrias and ventriculas) and         bleeding (due to capillary damage) and possibly kidney failure.         It is considered to be single-dose, or cumulative (depending on         concentration used; the common 0.075% bait concentration is         lethal to most rodents after a single intake of larger portions         of the bait), sub-chronic (death occurring usually within days         to one week after ingestion of the bait). Applied concentrations         are 0.075% cholecalciferol and 0.1% ergocalciferol when used         alone. There is an important feature of calciferols toxicology         which is that they are synergistic with anticoagulant toxicants.         This means that mixtures of anticoagulants and calciferols in         the same bait are more toxic than the sum of toxicities of the         anticoagulant and the calciferol in the bait so that a massive         hypercalcemic effect can be achieved by a substantially lower         calciferol content in the bait and vice-versa. More pronounced         anticoagulant/hemorrhagic effects are observed if calciferol is         present. This synergism is mostly used in baits low in         calciferol because effective concentrations of calciferols are         more expensive than effective concentrations of most         anticoagulants. The historically very first application of a         calciferol in rodenticidal bait was, in fact, the Sorex product         Sorexa® D (with a different formula than today's Sorexa® D) back         in the early 1970's, containing warfarin 0.025%+ergocalciferol         0.1%. Today, Sorexa® CD contains a 0.0025% difenacoum+0.075%         cholecalciferol combination. Numerous other brand products         containing either calciferols 0.075-0.1% (e. g. Quintox®,         containing 0.075% cholecalciferol) alone, or a combination of         calciferol 0.01-0.075% with an anticoagulant are marketed.

Miticides, Moluscicides and Nematicides.

Miticides are pesticides that kill mites. Antibiotic miticides, carbamate miticides, formamidine miticides, mite growth regulators, organochlorine, permethrin and organophosphate miticides all belong to this category. Molluscicides are pesticides used to control mollusks, such as moths, slugs and snails. These substances include metaldehyde, methiocarb and aluminium sulfate. A nematicide is a type of chemical pesticide used to kill parasitic nematodes (a phylum of worm). A nematicide is obtained from a neem tree's seed cake; which is the residue of neem seeds after oil extraction. The neem tree is known by several names in the world but was first cultivated in India since ancient times.

Antimicrobials

In the following examples, antimicrobials suitable for agrochemical compositions according to the present invention are given. Bactericidal disinfectants mostly used are those applying

-   -   active chlorine (i.e., hypochlorites, chloramines,         dichloroisocyanurate and trichloroisocyanurate, wet chlorine,         chlorine dioxide, etc.),     -   active oxygen (peroxides such as peracetic acid, potassium         persulfate, sodium perborate, sodium percarbonate and urea         perhydrate),     -   iodine (iodpovidone (povidone-iodine, Betadine), Lugol's         solution, iodine tincture, iodinated nonionic surfactants),     -   concentrated alcohols (mainly ethanol, 1-propanol, called also         n-propanol and 2-propanol, called isopropanol and mixtures         thereof; further, 2-phenoxyethanol and 1- and 2-phenoxypropanols         are used),     -   phenolic substances (such as phenol (also called “carbolic         acid”), cresols (called “Lysole” in combination with liquid         potassium soaps), halogenated (chlorinated, brominated) phenols,         such as hexachlorophene, triclosan, trichlorophenol,         tribromophenol, pentachlorophenol, Dibromol and salts thereof),     -   cationic surfactants such as some quaternary ammonium cations         (such as benzalkonium chloride, cetyl trimethylammonium bromide         or chloride, didecyldimethylammonium chloride, cetylpyridinium         chloride, benzethonium chloride) and others, nonquarternary         compounds such as chlorhexidine, glucoprotamine, octenidine         dihydrochloride, etc.),     -   strong oxidizers such as ozone and permanganate solutions;     -   heavy metals and their salts such as colloidal silver, silver         nitrate, mercury chloride, phenylmercury salts, copper sulfate,         copper oxide-chloride etc. Heavy metals and their salts are the         most toxic and environmentally hazardous bactericides and,         therefore, their use is strongly suppressed or forbidden;         further, also     -   properly concentrated strong acids (phosphoric, nitric,         sulfuric, amidosulfuric, toluenesulfonic acids) and     -   alcalis (sodium, potassium, calcium hydroxides) between pH<1         or >13, particularly below elevated temperatures (above 60° C.)         kill bacteria.

As antiseptics (i.e., germicide agents that can be used on human or animal body, skin, mucoses, wounds and the like), few of the above mentioned disinfectants can be used under proper conditions (mainly concentration, pH, temperature and toxicity toward man/animal). Among them, important are

-   -   Some properly diluted chlorine preparations (e. g. Daquin's         solution, 0.5% sodium or potassium hypochlorite solution,         pH-adjusted to pH 7-8, or 0.5-1% solution of sodium         benzenesulfochloramide (chloramine B)), some     -   iodine preparations such as iodopovidone in various galenics         (ointments, solutions, wound plasters), in the past also Lugol's         solution,     -   peroxides as urea perhydrate solutions and pH-buffered 0.1-0.25%         peracetic acid solutions,     -   alcohols with or without antiseptic additives, used mainly for         skin antisepsis,     -   weak organic acids such as sorbic acid, benzoic acid, lactic         acid and salicylic acid     -   some phenolic compounds such as hexachlorophene, triclosan and         Dibromol, and     -   cation-active compounds such as 0.05-0.5% benzalkonium, 0.5-4%         chlorhexidine, 0.1-2% octenidine solutions.

Bactericidal antibiotics kill bacteria; bacteriostatic antibiotics only slow down their growth or reproduction. Penicillin is a bactericide, as are cephalosporins. Aminoglycosidic antibiotics can act in both a bactericidic manner (by disrupting cell wall precursor leading to lysis) or bacteriostatic manner (by connecting to 30s ribosomal subunit and reducing translation fidelity leading to inaccurate protein synthesis). Other bactericidal antibiotics include the fluoroquinolones, nitrofurans, vancomycin, monobactams, co-trimoxazole, and metronidazole. In one or more embodiments, actives are those with systemic or partially systemic mode of action such as for example azoxystrobin.

Overall preferred are biocides selected from the group consisting of azoles, oxyfluorfen, propanil, chlorpyrifos, bifenthrin, novaluron, phenmedipham, deltamethrin, acetochlore, lambda-cyhalothrin, glyphosate and its salts, glufosinate and its salts, and mixtures of these species.

Oil Components

In a number of cases it is advantageous to add oil components (optional component c) to the biocide compositions in order to support the emulsification power of the products. Suitable products comprise Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C₆-C₂₂-fatty acids with linear or branched C₆-C₂₂-fatty alcohols or esters of branched C₆-C₁₃-carboxylic acids with linear or branched C₆-C₂₂-fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Also suitable are esters of linear C₆-C₂₂-fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C₁₈-C₃₈-alkylhydroxy carboxylic acids with linear or branched C₆-C₂₂-fatty alcohols, in particular Dioctyl Malate, esters of linear and/or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimertriol) and/or Guerbet alcohols, triglycerides based on C₆-C₁₀-fatty acids, liquid mono-/di-/triglyceride mixtures based on C₆-C₁₈-fatty acids, esters of C₆-C₂₂-fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C₂-C₁₂-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms (Cetiol® B) or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C₆-C₂₂-fatty alcohol carbonates, such as, for example, Dicaprylyl Carbonate (Cetiol® CC), Guerbet carbonates, based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and/or branched C₆-C₂₂-alcohols (e.g. Cetiol® AB), linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as, for example, dicaprylyl ether (Cetiol® OE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicone methicone grades, etc.), aliphatic or naphthenic hydrocarbons, such as, for example, squalane, squalene or dialkylcyclohexanes, and/or mineral oils. In one or more embodiments, the oil components/co-solvents show an ester structure preferably adipates (Cetiol® B, Agnique DiME 6), methyl esters of vegetable oils (Agnique® ME 18RD-F, Agnique® ME 12C-F), alkyl esters (Agnique® Ae 3-2EH), all products available in the market from Cognis GmbH.

Emulsifiers

In a number of cases it is advantageous to add emulsifiers (optional component d) to the biocide compositions in order to support the stability of the products. In one or more embodiments, the emulsifiers encompass non-ionic surfactants such as, for example:

-   -   products of the addition of 2 to 30 mol ethylene oxide and/or 0         to 5 mol propylene oxide onto linear C₈₋₂₂ fatty alcohols, onto         C₁₂₋₂₂ fatty acids and onto alkyl phenols containing 8 to 15         carbon atoms in the alkyl group;     -   C_(12/18) fatty acid monoesters and diesters of addition         products of 1 to 30 mol ethylene oxide onto glycerol;     -   glycerol mono- and diesters and sorbitan mono- and diesters of         saturated and unsaturated fatty acids containing 6 to 22 carbon         atoms and ethylene oxide addition products thereof;     -   addition products of 15 to 60 mol ethylene oxide onto castor oil         and/or hydrogenated castor oil;     -   polyol esters and, in particular, polyglycerol esters such as,         for example, polyglycerol polyricinoleate, polyglycerol         poly-12-hydroxystearate or polyglycerol dimerate isostearate.         Mixtures of compounds from several of these classes are also         suitable;     -   addition products of 2 to 15 mol ethylene oxide onto castor oil         and/or hydrogenated castor oil;     -   partial esters based on linear, branched, unsaturated or         saturated C_(6/22) fatty acids, ricinoleic acid and         12-hydroxystearic acid and glycerol, polyglycerol,         pentaerythritol, -dipentaerythritol, sugar alcohols (for example         sorbitol), alkyl glucosides (for example methyl glucoside, butyl         glucoside, lauryl glucoside) and polyglucosides (for example         cellulose);     -   alkoxylatation products of saccharose esters     -   mono-, di and trialkyl phosphates and mono-, di- and/or         tri-PEG-alkyl phosphates and salts thereof;     -   wool wax alcohols;     -   polysiloxane/polyalkyl polyether copolymers and corresponding         derivatives;     -   mixed esters of pentaerythritol, fatty acids, citric acid and         fatty alcohol and/or mixed esters of C₆₋₂₂ fatty acids, methyl         glucose and polyols, preferably glycerol or polyglycerol,     -   polyalkylene glycols and     -   glycerol carbonate.

The addition products of ethylene oxide and/or propylene oxide onto fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or onto castor oil are known commercially available products. They are homologue mixtures of which the average degree of alkoxylation corresponds to the ratio between the quantities of ethylene oxide and/or propylene oxide and substrate with which the addition reaction is carried out. C_(12/18) fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known as lipid layer enhancers for cosmetic formulations. The emulsifiers are described in more detail as follows:

Partial Glycerides

Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric acid diglyceride, malic acid monoglyceride, malic acid diglyceride and technical mixtures thereof which may still contain small quantities of triglyceride from the production process. Addition products of 1 to 30, and specifically 5 to 10, mol ethylene oxide onto the partial glycerides mentioned are also suitable.

Sorbitan Esters

Suitable sorbitan esters are sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof. Addition products of 1 to 30, and specifically 5 to 10, mol ethylene oxide onto the sorbitan esters mentioned are also suitable.

Polyglycerol Esters

Typical examples of suitable polyglycerol esters are Polyglyceryl-2 Dipolyhydroxystearate (Dehymuls® PGPH), Polyglycerin-3-Diisostearate (Lameform® TGI), Polyglyceryl-4 Isostearate (Isolan® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Behind), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403), Polyglyceryl Dimerate Isostearate and mixtures thereof. Examples of other suitable polyolesters are the mono-, di- and triesters of trimethylol propane or pentaerythritol with lauric acid, cocofatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like, optionally reacted with 1 to 30 mol ethylene oxide.

Alk(en)yl Oligoglycosides

The alkyl or alkenyl oligoglycosides representing emulsifiers may be derived from aldoses or ketoses containing 5 or 6 carbon atoms, specifically glucose. Accordingly, in one or more embodiments, the alkyl and/or alkenyl oligoglycosides are alkyl or alkenyl oligoglucosides. These materials are also known generically as “alkyl polyglycosides” (APG). The alk(en)yl oligoglycosides according to the invention correspond to formula (II):

R⁵O[G]_(p)  (II)

wherein R⁵ is an alkyl or alkenyl radical having from 6 to 22 carbon atoms, G is a sugar unit to having 5 or 6 carbon atoms and p is a number from 1 to 10. The index p in general formula (II) indicates the degree of oligomerisation (DP degree), i.e. the distribution of mono- and oligoglycosides, and is a number of 1 to 10. Whereas p in a given compound must always be an integer and, above all, may assume a value of 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined calculated quantity which is mostly a broken number. Alk(en)yl oligoglycosides having an average degree of oligomerisation p of 1.1 to 3.0 are preferably used. Alk(en)yl oligoglycosides having a degree of oligomerisation below 1.7 and, more particularly, between 1.2 and 1.4 are preferred from the applicational point of view. The alkyl or alkenyl radical R⁵ may be derived from primary alcohols containing 4 to 22 and preferably 8 to 16 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof such as are formed, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Alkyl oligoglucosides based on hydrogenated C₈-C₁₆ coconut oil alcohol having a DP of 1 to 3 are preferred. Also suitable are alkoxylation products of alkyl oligoglucosides, for example adducts of 1 to 10 moles ethylene oxide and/or 1 to 5 moles propylene oxide to C₈-C₁₀ or C₁₂-C₁₈ alkyl oligoglucoside having a DP between 1.2 and 1.4.

Alkoxylated Vegetable Oils

Suitable emulsifiers are castor oil, rape seed oil, soy been oil ethoxylated with 3 to 80 moles ethylene oxide (Agnique®CSO 35, Agnique®SBO 10, Agnique®SBO 60))

Alkoxylated Copolymers

Typical copolymers are ethoxylated and propoxylated block and/or random polymers of C₂-C₂₂ linear or branched alcohols.

Miscellaneous Emulsifiers

Typical anionic emulsifiers are aliphatic C₁₂₋₂₂ fatty acids such as palmitic acid, stearic acid or behenic acid, for example, and C₁₂₋₂₂ dicarboxylic acids such as azelaic acid or sebacic acid, for example. Other suitable emulsifiers are zwitterionic surfactants. Zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Ampholytic surfactants are also suitable emulsifiers. Ampholytic surfactants are surface-active compounds which, in addition to a C₈₁₁₈ alkyl or acyl group, contain at least one free amino group and at least one —COOH— or —SO₃H— group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, Nalkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. In one or more embodiments, the ampholytic surfactants are selected from N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C_(12/18) acyl sarcosine.

Biocide Compositions

Depending on the nature of the biocide, the products may show the following compositions:

-   (a) about 0.1% b.w. to about 99% b.w., in a specific embodiment     about 15% b.w. to about 70% b.w., and in a more specific embodiment     about 20% b.w. to about 45% b.w., esters and/or amides of     pyroglutamic acid, -   (b) about 1% b.w. to about 99.1% b.w., in a specific embodiment     about 5% b.w. to about 75% b.w., and in a more specific embodiment     about 15% b.w. to about 40% b.w., biocides, -   (c) 0 to about 50, in a specific embodiment about 5 to about 30 and     in a more specific embodiment about 10 to about 25% b.w. oil     components/co-solvents and -   (d) 0% b.w. to about 15% b.w., and in a specific embodiment about 5     to about 10% b.w. emulsifiers,     with the proviso that the numbers, optionally with water and/or     polyols, add to 100% b.w. The compositions are pesticides     concentrates to be diluted with water to give aqueous formulations     for end-users comprising about 0.5 to about 5, in a specific     embodiment about 0.5 to about 1% of the active matter represented by     the concentrate.

INDUSTRIAL APPLICATION

A final embodiment of the present invention is related to the use of esters and/or amides of pyroglutamic acid, in particular pyroglutamic acid methyl ester, pyroglutamic acid ethyl ester, pyroglutamic acid propyl ester(s), pyroglutamic acid butyl ester(s), pyroglutamic acid n-octyl ester, pyroglutamic-2-ethylhexyl ester, pyroglutamic acid furfuryl ester, pyroglutamic acid tetrahydrofurfuryl ester, pyroglutamic acid dimethyl amide, pyroglutamic acid diethyl amide, pyroglutamic acid dipropyl amide, pyroglutamic acid dibutyl amide, pyroglutamic acid di-n-octyl amide, pyroglutamic acid di-2-ethylhexyl amide, and their mixtures, as solvents or dispersants for biocides.

EXAMPLES Examples 1 to 5 Stability

Several emulsifiable concentrates have been designed and prepared by mixing biocides, dimethylamides, co-solvents and emulsifiers. The concentrates were subsequently diluted at 5% in water. Characteristics of 5% b.w. emulsions in different water hardness and stored at 20° C. for 24 h were assessed. The stability of the emulsions was determined as a function of time. As far as layering is concerned (++) means “no layering” and (+) “about 1 ml layering”. For opacity (++) means an opaque white emulsion and (+) a slightly opalescent emulsion. The results are compiled in Table 1. The amounts reflect the composition of the concentrates.

TABLE 1 Stability of biocide compositions Composition [% b.w.] 1 2 3 4 5 Tebuconazole 25 25 — — — Oyfluorfen — — 20 23 Pyroglutamic acid di-2- 35 — — 45 — ethylhexyl ester Pyroglutamic acid tetrahydro- — 35 — — 45 furfuryl ester Pyroglutamic acid dimethylamide — — 32 — — Dibutyl Adipate — — — 25 22 2Ethylhexyl Lactate 35 35 33 — Saccharose ester + 10EO 10 — — 10 Agnique ® MBL 510 — 10 — —  8 Agnique ® MBL 520 — — — —  2 Agnique ® CSO 30 — —  7 — — Comperlan ® KD — —  3 — — Appearance Clear Clear Clear Clear Clear Emulsion properties spontaneously ++ ++ ++ ++ ++ layering after 1 h ++ ++ ++ ++ ++ opacity after 1 h ++ ++ + + + layering after 2 h + + + ++ ++ opacity after 2 h ++ ++ + + + layering after 24 h ++ + + + +

The examples indicate that excellent emulsification behaviour is obtained as a result of optimized solvents mixture and emulsifier systems.

Example 6 Comparative Examples C1 and C2 Solubility

Solubility of two fungicides, one herbicide and two insecticides in different dialkyl amides at 25° C. was tested; the active solubility has been 25% b.w. The results, including minimum target solubility for each biocide is presented in Table 2.

TABLE 2 Solubility of biocides [% b.w.] Ex. Solvents Tebucanozole Epoxiconazole Oxfluoren Novaluron Imidacloprid Minimum 30 12.5 25 15 20 target solubility 6 Pyroglutamic 40 20 35 23 20 acid tetrahydro- furfuryl ester C1 C₈-C₁₀ fatty 38 9 31 32 4 acid dimethylamide C2 Lactic acid di- 35 15 23 22 12 methyl amide 

What is claimed is:
 1. A biocide composition, comprising (a) an ester of pyroglutamic acid according to general formula (I)

wherein X is O[AO]_(n)R¹, [AO] is a C₂-C₄ alkylene oxide unit, n is 0 or an integer of 1 to 100, R¹ represents hydrogen, an alkyl or alkenyl radical having 1 to 22 carbon atoms or a (tetrahydro)furfuryl residue, and (b) a biocide; (c) optionally an oil component or a co-solvent; and (d) optionally an emulsifier.
 2. (canceled)
 3. The composition according to claim 1, wherein component (a) comprises an ester selected from the group consisting of pyroglutamic acid methyl ester, pyroglutamic acid ethyl ester, pyroglutamic acid propyl ester(s), pyroglutamic acid butyl ester(s), pyroglutamic acid n-octyl ester, pyroglutamic-2-ethylhexyl ester, pyroglutamic acid furfuryl ester, pyroglutamic acid tetrahydrofurfuryl ester, and mixtures thereof.
 4. (canceled)
 5. The composition according to claim 1, wherein the biocide is selected from the group consisting of herbicides, fungicides, insecticides, and plant growth regulators.
 6. The composition according to claim 1, wherein the biocide is selected from the group consisting of azoles, oxyfluorfen, propanil, chlorpyrifos, bifenthrin, novaluron, phenmedipham, deltamethrin, acetochlore, lambda-cyhalothrin, glyphosate and its salts, and glufosinate and its salts.
 7. The composition according to claim 1, further comprising (c) an oil component or a co-solvent.
 8. The composition according to claim 1, further comprising (d) an emulsifier.
 9. The composition according to claim 1, wherein the composition comprises (a) 0.1% b.w. to 99% b.w. the ester of pyroglutamic acid, (b) 1% b.w. to 99.1% b.w. the biocide, (c) 0% b.w. to 50% b.w. the oil component or the co-solvent, and (d) 0% b.w. to 15% b.w. the emulsifier with the proviso that the amounts add, optionally with water and/or polyols, to 100% b.w.
 10. The composition according to claim 1, wherein the composition has an active matter content of 5% b.w. to 50% b.w.
 11. A method of dispersing a biocide, the method comprising using an ester of pyroglutamic acid as a solvent or dispersant.
 12. The method of claim 2, wherein the ester of pyroglutamic acid is selected from the group consisting of pyroglutamic acid methyl ester, pyroglutamic acid ethyl ester, pyroglutamic acid propyl ester(s), pyroglutamic acid butyl ester(s), pyroglutamic acid n-octyl ester, pyroglutamic-2-ethylhexyl ester, pyroglutamic acid furfuryl ester, pyroglutamic acid tetrahydrofurfuryl ester, and mixtures thereof.
 13. The method of claim 11, wherein the biocide is selected from the group consisting of herbicides, fungicides, insecticides, and plant growth regulators.
 14. The method of claim 11, wherein the biocide is selected from the group consisting of azoles, oxyfluorfen, propanil, chlorpyrifos, bifenthrin, novaluron, phenmedipham, deltamethrin, acetochlore, lambda-cyhalothrin, glyphosate and its salts and glufosinate and its salts. 